Etching solution for copper/molybdenum-based multilayer thin film

• US 9,365,770 B2
• Filed: 07/25/2012
• Issued: 06/14/2016
• Est. Priority Date: 07/26/2011
• Status: Active Grant

• Current Assignee: Mitsubishi Gas Chemical Company Incorporated (Mitsubishi Electric Corporation)
• Original Assignee: Mitsubishi Gas Chemical Company Incorporated (Mitsubishi Electric Corporation)
• Inventors: Okabe, Satoshi, Adaniya, Tomoyuki, Maruyama, Taketo
• Primary Examiner(s): Roman, Angel
• Application Number:
  US14/235,290
• Publication Number:
  US 20140162403A1
• Time in Patent Office: 1,420 Days
• Field of Search: None
• US Class Current: 1/1
• CPC Class Codes: C09K 13/06 with organic material
• CPC Class Codes: C23F 1/18 for etching copper or alloys thereof
• CPC Class Codes: C23F 1/26 for etching refractory metals
• CPC Class Codes: H01L 21/32134 by liquid etching only
• CPC Class Codes: H01L 21/465 Chemical or electrical treatment, e.g. electrolytic etching to form insulating layers H01L21/469
• CPC Class Codes: H01L 29/45 Ohmic electrodes
• CPC Class Codes: H01L 29/458 for thin film silicon, e.g. source or drain electrode
• CPC Class Codes: H01L 29/66765 Lateral single gate single channel transistors with inverted structure, i.e. the channel layer is formed after the gate
• CPC Class Codes: H01L 29/66969 of devices having semiconductor bodies not comprising group 14 or group 13/15 materials comprising selenium or tellurium in uncombined form other than as impurities in semiconductor bodies of other materials, comprising cuprous oxide or cuprous iodide H01L21/02365
• CPC Class Codes: H01L 29/7869 having a semiconductor body comprising an oxide semiconductor material, e.g. zinc oxide, copper aluminium oxide, cadmium stannate

Abstract

The present invention relates to an etching solution being capable of selectively etching a copper/molybdenum-based multilayer thin film with respect to a semiconductor device having an oxide semiconductor layer and a copper/molybdenum-based multilayer thin film, wherein the etching solution comprises (A) hydrogen peroxide, (B) an inorganic acid containing no fluorine atom, (C) an organic acid, (D) an amine compound having 2 to 10 carbon atoms, and having an amino group and at least one group selected from an amino group and a hydroxyl group, (E) an azole, and (F) a hydrogen peroxide stabilizer, and has a pH of 2.5 to 5, as well as an etching method using the etching solution for selectively etching a copper/molybdenum-based multilayer thin film from a semiconductor device having an oxide semiconductor layer and a copper/molybdenum-based multilayer thin film.

Claims

1. An etching solution, comprising:

(A) hydrogen peroxide;

(B) an inorganic acid comprising no fluorine atom;

(C) an organic acid;

(D) an amine compound having 2 to 10 carbon atoms, and comprising a first amino group and at least one selected from the group consisting of a second amino group and a hydroxyl group;

(E) an azole; and

(F) a hydrogen peroxide stabilizer,

wherein the etching solution has a pH of 2.5 to 5.

2. The etching solution according to claim 1, wherein the inorganic acid (B) is at least one of sulfuric acid and nitric acid.

3. The etching solution according to claim 1, wherein the organic acid (C) is at least one selected from the group consisting of succinic acid, glycolic acid, lactic acid, malonic acid and malic acid.

4. The etching solution according to claim 1, wherein the amine compound (D) is at least one selected from the group consisting of ethanolamine, 1-amino-2-propanol and N,N-diethyl-1,3-propanediamine.

5. The etching solution according to claim 1, wherein the azole (E) is 5-amino-1H-tetrazole.

6. The etching solution according to claim 1, wherein the hydrogen peroxide stabilizer (F) is phenylurea.

7. The etching solution of claim 1, comprising:

(A) 3 to 10% by mass of the hydrogen peroxide (A);

(B) 0.01 to 5% by mass of the inorganic acid (B) containing no fluorine atom;

(C) 1 to 15% by mass of the organic acid (C);

(D) 1 to 10% by mass of the amine compound (D);

(E) 0.001 to 1% by mass of the azole (E); and

(F) 0.01 to 0.5% by mass of the hydrogen peroxide stabilizer.

8. The etching solution according to claim 1, further comprising copper ions in an amount of 100 to 8,000 ppm.

13. The etching solution of claim 1, which can selectively etch a copper/molybdenum-based multilayer thin film with respect to a semiconductor device comprising an oxide semiconductor layer and the copper/molybdenum-based multilayer thin film.

14. The etching solution of claim 7, which can selectively etch a copper/molybdenum-based multilayer thin film with respect to a semiconductor device comprising an oxide semiconductor layer and the copper/molybdenum-based multilayer thin film.

15. The etching solution according to claim 13, wherein the oxide semiconductor layer is an oxide semiconductor layer comprising at least one of indium, gallium and zinc.

16. The etching solution according to claim 15, wherein the oxide semiconductor layer is an oxide semiconductor (IGZO) layer comprising indium, gallium and zinc.

9. An etching method for selectively etching a copper/molybdenum-based multilayer thin film of a semiconductor device comprising an oxide semiconductor layer and the copper/molybdenum-based multilayer thin film, the etching method comprising;

contacting the semiconductor device with an etching solution, comprising;

(A) hydrogen peroxide;

(B) an inorganic acid comprising no fluorine atom;

(C) an organic acid;

(D) an amine compound having 2 to 10 carbon atoms, and comprising a first amino group and at least one selected from the group consisting of a second amino group and a hydroxyl group;

(E) an azole; and

(F) a hydrogen peroxide stabilizer;

wherein the etching solution has a pH of 2.5 to 5.

10. The etching method according to claim 9, wherein the oxide semiconductor layer is an oxide semiconductor layer comprising at least one of indium, gallium and zinc.

11. A method for producing a semiconductor device, the method comprising:

contacting a semiconductor device comprising an oxide semiconductor layer and a copper/molybdenum-based multilayer thin film with an etching solution, comprising;

(A) hydrogen peroxide;

(B) an inorganic acid comprising no fluorine atom;

(C) an organic acid;

(D) an amine compound having 2 to 10 carbon atoms, and comprising a first amino group and at least one selected from the group consisting of a second amino group and a hydroxyl group;

(E) an azole; and

(F) a hydrogen peroxide stabilizer;

wherein the etching solution has a pH of 2.5 to 5.

12. The method according to claim 11, wherein the oxide semiconductor layer is an oxide semiconductor layer comprising at least one of indium, gallium and zinc.